Chang Xijun, Wang Yuman, Zhao Ran
Department of Chemistry, Lanzhou University, 730000, Lanzhou, Gansu, China.
Anal Bioanal Chem. 2003 Oct;377(4):757-62. doi: 10.1007/s00216-003-2129-1. Epub 2003 Aug 12.
Poly(acryl p-aminobenzenesulfonamideamidine- p-aminobenzenesulfonylamide) chelating fiber containing "S", "N", and "O" elements was synthesized from polyacrylonitrile fiber and p-aminobenzene sulfonamide and used to enrich and separate trace Bi(III), Hg(III), Au(III), and Pd(IV) ions from wastewater and ore sample solution. The enrichment acidity, flow rate, elution conditions, reuse, interference ions, saturated adsorption capacity, constant of adsorption rate, analytical accuracy, and actual samples on chelating fiber were investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES) with satisfactory results. Solutions of 100 ng mL(-1) of Bi(III), Hg(III), Au(III), and Pd(IV) ions can be enriched quantitatively by this chelating fiber at a rate of 1.0 mL min(-1) at pH 4 and desorbed quantitatively with 20 mL of 0.25 M HCl and 2% CS(NH(2))(2) solution at 50 degrees C (with recovery >/=97%). When the chelating fiber was reused for 20 times, the recoveries of the analyzed ions enriched by the fiber were still over 95% (except for Hg(III)). One thousand-fold excesses of Mn(2+), Ca(2+), Zn(2+), Mg(2+), Fe(3+), Cu(2+), Ni(2+), Al(3+), and Ba(2+) ions and thousands-fold excesses of Na(+ )and K(+) cause little interference in the pre-concentration and determination of the analyzed ions. The saturated adsorption capacity of Bi(III), Hg(III), Au(III), and Pd(IV) was 4.850 x 10(-4), 3.235 x 10(-4), 2.807 x 10(-4), and 3.386 x 10(-4) mol g(-1), respectively. The constants of adsorption rate were 0.409 min(-1) for Bi, 0.122 min(-1) for Hg, 0.039 min(-1) for Au, and 0.080 min(-1 )for Pd. The relative standard deviations (RSDs) for the enrichment and determination of 10 ng mL(-1) Bi(III), Hg(III), Au(III), and Pd(IV) were lower than 2.3%. The results obtained for these ions in actual samples by this method were basically in agreement with the given values with average errors of less than 1.0%. FT-IR spectra shows that the existence of -SO(2)-Ar, -H(2)N-Ar, O=C-NH-, HN=C-NH-, and -HN-SO(2) functional groups are verified in the chelating fiber. From the FT-IR spectroscopy, we can see that Hg(III), Au(III), and Pd(IV) are mainly combined with nitrogen and sulfur (or oxygen), and Bi(III) is mainly combined with nitrogen (or oxygen) of the groups to form a chelating complex.
由聚丙烯腈纤维与对氨基苯磺酰胺合成了含“S”“N”“O”元素的聚(对氨基苯磺酰胺脒 - 对氨基苯磺酰胺)螯合纤维,并用于从废水和矿石样品溶液中富集和分离痕量Bi(III)、Hg(III)、Au(III)和Pd(IV)离子。通过电感耦合等离子体发射光谱法(ICP - OES)研究了螯合纤维的富集酸度、流速、洗脱条件、重复使用性、干扰离子、饱和吸附容量、吸附速率常数、分析准确度以及实际样品,结果令人满意。该螯合纤维能在pH 4、流速为1.0 mL min⁻¹的条件下,以100 ng mL⁻¹的速率定量富集Bi(III)、Hg(III)、Au(III)和Pd(IV)离子溶液,并在50℃下用20 mL 0.25 M HCl和2% CS(NH₂)₂溶液定量洗脱(回收率≥97%)。当螯合纤维重复使用20次时,除Hg(III)外,纤维富集的分析离子回收率仍超过95%。1000倍过量的Mn²⁺、Ca²⁺、Zn²⁺、Mg²⁺、Fe³⁺、Cu²⁺、Ni²⁺、Al³⁺和Ba²⁺离子以及数千倍过量的Na⁺和K⁺离子对分析离子的预富集和测定干扰很小。Bi(III)、Hg(III)、Au(III)和Pd(IV)的饱和吸附容量分别为4.850×10⁻⁴、3.235×10⁻⁴、2.807×10⁻⁴和3.386×10⁻⁴ mol g⁻¹。Bi的吸附速率常数为0.409 min⁻¹,Hg为0.122 min⁻¹,Au为0.039 min⁻¹,Pd为0.080 min⁻¹。对10 ng mL⁻¹ Bi(III)、Hg(III)、Au(III)和Pd(IV)进行富集和测定的相对标准偏差(RSD)低于2.3%。该方法对实际样品中这些离子的测定结果与给定值基本一致,平均误差小于1.0%。傅里叶变换红外光谱(FT - IR)表明,螯合纤维中存在 -SO₂ - Ar、 -H₂N - Ar、O = C - NH -、HN = C - NH - 和 -HN - SO₂官能团。从FT - IR光谱可以看出,Hg(III)、Au(III)和Pd(IV)主要与氮和硫(或氧)结合,Bi(III)主要与这些基团的氮(或氧)结合形成螯合配合物。